DE1003502B - Additives to fuels and distillate heating oils - Google Patents

Description

GERMAN

It is known that metals such as copper can get into fuels in small amounts, e.g. B. when the fuels contain traces of naphthenic acids or phenols and with metal parts such as valves or sieves made of brass, come into contact during their manufacture or processing. Even with refining of fuels such as B. cracking and polymer gasoline, with copper salts often remain small amounts Copper dissolved back in the fuels. The dissolved metals are effective even in very low concentrations unfavorable to the shelf life of fuels such as cracking, reforming, polymer gasoline, distillate heating oils, Jet fuels and the like. Above all, they impair the protective effect of "rubber inhibitors" that are used for Improving the shelf life of such fuels adds.

It is also known by adding condensation products of salicylaldehyde with diamines, so-called Schiff bases to prevent the adverse effects of traces of metal on fuels. So z. B. that Copper bound by these compounds in the form of a chelate and inactivated so that it is not harmful Can have more effect. Such a chelate has the following constitutional formula:

V-CH = N-CH ₂ -CH ₂ -N =

Additives to fuels
and distillate heating oils

However, all previously known metal deactivators based on salicylaldehyde and diamines are crystallized and with the help of solubilizers such as benzene, toluene, xylene, butanol, acetone, etc., first in Solution are brought before you can add them to a fuel. The solubility in these solubilizers however, it is only limited. For example, benzene does not dissolve more than 80 g at room temperature crystallized disalicylethylenediamine and 11 acetone only about 40 g of the same product. In addition, some of the known metal deactivators, such as the Schiff's base made from salicylaldehyde and ethylenediamine, despite the use of solubilizers in many propellants

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Günther Nottes and Dr. Otto Stichnoth,

Ludwigshafen / Rhine,
have been named as inventors

substances, especially at low temperatures, are very difficult to dissolve, which means that they can be used in winter or in aviation fuels at high altitudes. The use of solubilizers has furthermore the disadvantage that these often get into the fuels as undesirable accompanying substances and under certain circumstances change the required properties of the fuels.

It has now been found that the storage stability of fuels and distillate heating oils is particularly important can advantageously improve if you give them condensation products of salicylaldehyde and such polyamines added, which contain a bridging nitrogen atom in the molecule. The still free hydrogen atom on the bridge nitrogen can be represented by hydrogen, an alkyl group, e.g. B.

—CH ₃ , —C ₂ H ₅ , a cycloalkyl group, e.g. B. —C ₆ H ₁₁ , or the acetyl group CH ₃ CO— can be substituted. For the condensation with salicylaldehyde z. B. the following polyamines into consideration: dipropylenetriamine, methyldipropylenetriamine, propyldipropylenetriamine, acetyldipropylenetriamine. 1 mole of the Schiff base from di-propylenetriamine and salicylaldehyde binds 1 atom of copper according to the following formula:

= N-CH ₂ -CH ₂ -CH ₂ -N-CH ₂ -Ch ₂ -CH ₂ -N =

l-O-

R = H, CH ₃ , C ₂ H ₆ , etc.

Surprisingly, it has been shown that the condensation products mentioned in any ratio in the conventional fuels are soluble and still have a very good solubility even at very low temperatures. So is z. B. a gasoline that is in a catalytic cracking

609 837/221

plant was obtained at room temperature in each Miscible with disalicylidene-N-di-propylenetriamine, while the same gasoline at the same temperature only 0.076% of the crystallized disalicylidene ethylenediamine able to solve.

In a gas oil fraction at -5 ° there are 30 g of disalicylidene-N-methyl-di-propylenetriamine soluble per liter, on the other hand the solubility of crystallized disalicylidene ethylenediamine is practically zero in the same gas oil fraction at the same temperature.

The good solubility of the claimed metal deactivators can also be seen from the following table, which shows that these products are present in gas oil in significant amounts Temperatures are soluble at which, for example, the disalicylide of ethylenediamine is completely insoluble.

Metal deactivator,
still, soluble in gas oil
(naphthenic)
% Disalicylid
N-methyl-dipropylene-
triamine Disalicylid
N-ethyl-dipropylene-
triamine Disalicylid
N-propyl-dipropylene-
triamine 10
5
2
1 + 8 ° C
0 ° C
-12 ° C
-25 ° C -15 ° C
-28 ⁰ C
-49 ° C
below -50 ° C -21 ° C
-33 ° C
below -60 ° C
Oil solidifies

The claimed metal deactivators can be shipped without solubilizers, which means transport costs be saved. The copper-binding effect of these Schiff bases is the same as that of the previous ones used crystallized products.

if it is with the same amount of disalicylidene-N-methyldi-propylenetriamine was displaced. The product used according to the invention is thus in its deactivating It works just as well as the metal deactivators used so far with the help of solubilizers.

example

A cracked gasoline, which was freed from harmful mercaptans by refining with copper salts, resulted when using one of the usual rubber inhibitors after adding 0.001% disalicylidenediamine after treatment an ASTM glass cup test of 10 mg / 100 ecm in the 8-hour ASTM bomb test.

The same gasoline gave a glass cup test of 8 mg / 100 ecm under the same test conditions,

Claims (1)

PATENT CLAIM: Use of condensation products of salicylaldehyde and those polyamines that have a The molecule contains bridging nitrogen atoms as additives to fuels and distillate heating oils. Considered publications:
U.S. Patent No. 2,622,018. © 60 »837/221 2.57